Vol.6 (2016) No. 3 ISSN: 2088-5334

Liquid Smoke Production Quality from Raw Materials Variation and Different Pyrolysis Temperature I Ketut Budaraga#, Arnim*, Yetti Marlida*, Usman Bulanin1 # Agricultural Technology Department, Faculty of Agricultural Ekasakti University, Padang 25163 Indonesia E-mail: [email protected]/[email protected]

* Animal Production Department, Faculty of Animal Husbandry Andalas University, Padang, Indonesia E-mail: [email protected] and [email protected]

1 Fisheries Cultivation Department, Faculty of Fisheries Bung Hatta University, Padang, Indonesia E-mail: [email protected]

Abstract— This research is intended to know liquid smoke chemical and physical characteristics quality acquired from pyrolysis from various raw materials with different temperature level. The making of liquid smoke is done through pyrolysis process with temperature level 100±10oC; 200±10oC; 300±10oC; and 400±10oC for 5 hour. This research is done experimentally by using complete random design on factorial pattern 3 x 4 with 3 repetition. Factor A is raw materials type that consists of coconut fibre, coconut shell and cinnamon while factor B is temperature level. The observed parameter consists of liquid smoke physical characteristic that consists of equipment performance, density, rendement, degree of acidity and chemical characteristic that consists of water-content, titrated acid total, phenol-content, carbonyl-content and benzo(a)pyren-content. The result of research shows that there is a very actual interaction (P<0,05) between using raw materials type with pyrolysis temperature level toward equipment performance, density, rendement, degree of acidity, water-content, titrated acid total, phenol-content, carbonyl-content and benzo(a)pyren-content. The best liquid smoke production quality can be found in raw materials cinnamon treatment on temperature level 400±10oC, which is pyrolysis equipment performance 16,29 ml/hour.meter, density 1,017 g/ml, rendement 38,78%, pH 3,503, titrated acid total 0,72 %, phenol-content 0,57 %, carbonyl-content 4,13 %, benzo(a)pyren-content 0,04 ppm. Based on the result of this research, it can be concluded that using cinnamon with level pyrolysis temperature 400±10oC is better used rather than coconut fibre and coconut shell because of its lowest benzo(a)pyren-content.

Keywords— raw materials type; temperature; liquid smoke; physical characteristic; chemical characteristic.

and compound composition on liquid smoke product. The I. INTRODUCTION result of research is that teak wood dusts pyrolysis result An easy and simple technology that can be used is needed consist of p-guaiakol, 2 methoxy 4 propenil phenol, 2 in fulfilling the need of natural preservatives such as liquid methoxy 4 methyl phenol, 3,4,5 trimethoxy toluene and 1,3 smoke. That technology later can be used as an alternative to dimethoxy siringol which is the basic components of biofuel replace chemical preservatives that comes from [6]. While dominant compound from miswak wood and environmental raw materials such as coconut fibre, coconut acacia wood pyrolysis result consists of acetic acid and shell and cinnamon. Liquid smoke is acetic acid that is vanillin [7], and from organic waste is y-butyrolactone and acquired through pyrolysis process from material that 2-hydroxy 3 methyl 2 cyclopentene-1-on [4]. consists of cellulose, hemicellulose and lignin components The diversity of raw materials and liquid smoke [1]. production method result in complex chemical component Various raw materials have been used in the making of with various structure, reactivity and sensory activity [8]. liquid smoke among others by using cashew nut shell and While on pyrolysis, cellulose will experience hydrolysis that coconut fibre [2], coconut shell [3], organic waste [4], produces glucose and further reaction produces acetic acid, coconut shell and coconut fibre [5]. That raw materials water and a little bit of phenol [9]. Lignin in pyrolysis consist of enough cellulose and lignin contents. That result produces phenol compound and its derivatives and pyrolysis of research shows relationship between raw materials type on high temperature will produces tar. While on pyrolysis,

306 hemicellulose will produces furfuran, furan and carboxylic temperature difference shows the interaction and actual acid. Various compounds with diverse compositions can be influence to equipment performance. acquired from pyrolysis process, apart from that raw materials type along with pyrolysis operation condition is TABLE I estimated to have influence on chemical and physical THE AVERAGE OF LIQUID SMOKE EQUIPMENT PERFORMANCE ON RAW MATERIALS WITH DIFFERENT PYROLYSIS TEMPERATURE FOR 5 HOURS characteristics of liquid smoke. The purpose from this research is to know the quality of liquid smoke production from chemical and physical characteristics with pyrolysis on various raw materials combined with different pyrolysis temperature level.

II. MATERIAL AND METHOD Material and Equipment. Raw material such coconut fibre waste, coconut shell come from Pasar Raya Padang and cinnamon with its bark condition taken in dry condition is acquired from cinnamon farmer in Tanah Datar. Chemical material that is used to analysis between 0,1 N NaOH, distilled water, phenolphthalein, Na2CO3, Folin Ciocalteu this, DMSO, petri dish for nutrients. To analysis smoke component, it uses methanol, helium gas, Whatman No. 42 filter paper. Equipment that is used in pyrolysis consists of one set laboratory scale liquid smoke maker that consists of stainless steel kiln with 3 kg capacity, condenser unit 14 meter length, cooling pipe by using glass pipe, distillate Note : Superscript letter that is different on average column shows actual bottle (container liquid smoke), gas stove, water pump, difference (P<0,05) water drum, water hose for condenser cooler, ball valve, PVC pipe, pole, clamp, thermometer, stopwatch, measuring Further test with Tukey on ά = 0,5 shows the actual cup, 10 ml microliters syringe, luer key syringe with difference between the combination of raw materials diameter 25 mM from 0,45 mm PVDF, lock syringe 10 ml treatment with pyrolysis temperature. The higher pyrolysis vial B x 40 mm and GC MS. and other equipments that are temperature then the tendency the tendency of equipment used, such as 1 (one) aquarium set, weights, thermos bottle, performance will become higher, it is caused by liquid patrialis cup, electric stove, filter paper, oven, distillation smoke raw materials components decomposition. If equipment, analytic scales, oven, porcelain bowl, desiccator, equipment performance is reviewed from raw materials, it filter, pH meter, 125 ml Erlenmeyer and 500 ml glass, filter turns out that coconut fibre raw materials caused the result of paper, Soxhlet, tube, centrifuge tube, micro buret, pipette, lowest equipment performance like in the figure 1 below. volumetric flask pipette 250 ml, centrifuge, spectrophotometer, pycnometer This research uses factorial experiment 3 x 4 with three repetition in complete random design (RAL). The first factor consists of 3 (three) level of liquid smoke raw materials source like cinnamon, coconut shell, cinnamon, and the second factor consists of 4 (four) level pyrolysis temperature 100 ± 10oC; 200 ± 10oC; 300 ± 10oC; from 400 ± 10°C for 5 hour. The data is analyzed by using variant analysis (ANOVA), if it is different significantly, then it will be tested the difference between the treatment with Tukey Test (BNJ) on significance level 5 percent [10]. The entire calculation is done with Statistic 8 program.

Fig. 1 Liquid smoke maker equipment performance based on treatment III. RESULT AND DISCUSSION combination of raw materials difference and different pyrolysis temperature

A. Pyrolysis Equipment Performance Based on figure 1, generally equipment performance will Liquid smoke maker equipment performance basically is be different with different pyrolysis temperature, the based on distillation volume accumulated every one hour tendency shows with the higher pyrolysis temperature then that is produced by condenser, like the formulation used by the acquired volume distillation will cause higher equipment Hanendyo (11) shown on Table 1 below. performance. The result in this research is not actually Based on the analysis result of liquid smoke maker different with the result of research by Tranggono et al. [12], pyrolysis equipment performance ranges from 5,79% to which is 52,85 %. They uses raw materials of various wood 16.29%. The result of variance investigation shows that types and coconut shell also it is done on burning combination of raw materials factor with pyrolysis temperature 350 - 400°C.

307 Condensate that is newly produced has dark brown color 1) Density (g/ml): Liquid smoke density is a comparison specifically to coconut fibre liquid smoke, while coconut between the liquid smoke weights to raw materials weight. shell and cinnamon liquid smoke color is light brown like in Liquid smoke density shows the level of liquid smoke figure 2. Dark brown color from liquid smoke is caused by density, it means that the higher liquid smoke density then its carbonyl-content. The higher its carbonyl-content, the its density will become higher. Based on table 2 above that higher its brown color potency [13], [14]. Coconut fibre statistically the average of coconut fibre raw materials liquid smoke has the most brown color so that it can be treatment combination with pyrolysis temperature 100 ± concluded that in that liquid smoke consists lots of carbonyl. 10°C with 200 oC ± 10°C has actual difference, it also has Cinnamon coconut shell liquid smoke has pungent smell actual difference with the temperature of 3000C ± 10°C and like the smell from liquid smoke produced by burning the temperature of 4000C ± 10°C. Similar thing also happens cinnamon. This pungent smell comes from phenol to raw materials coconut shell treatment combination with compound in the liquid smoke [15]. The result of liquid pyrolysis temperature of 100 ± 10°C with 2000C ± 10°C has smoke from coconut fibre, coconut shell and cinnamon can shown actual difference, it also has actual difference with be seen on figure 2 below. temperature 3000C ± 10°C and temperature 4000C ± 10°C. For cinnamon treatment combination with pyrolysis temperature of 100 ± 10°C with 2000C ± 10°C has shown actual difference, it also shows actual difference with temperature 3000C ± 10°C and temperature 4000C ± 10°C. This difference is suspected that pyrolysis temperature has influence to liquid smoke component decomposition so that it has difference statistically. Liquid smoke density on Table 2 shows that there is Fig. 2 Liquid smoke color of coconut fibre, coconut shell and Cinnamon actual interaction (P <0.05) between factor A (raw materials type) with factor B (pyrolysis level temperature) on liquid smoke after distillation. Figure of liquid smoke density on B. Physical characteristic from liquid smoke raw materials treatment combination with pyrolysis Physical characteristic on the result of liquid smoke temperature like figure 3 below. production research from several raw materials that consists of coconut fibre, coconut shell and cinnamon with different pyrolysis temperature can be seen on table 2 below.

TABLE II THE AVERAGE OF LIQUID SMOKE PHYSICAL CHARACTERISTIC FROM DIFFERENT TREATMENT COMBINATION OF RAW MATERIALS WITH DIFFERENT PYROLYSIS TEMPERATURE

Fig. 3 Liquid Smoke Density Average from Various Raw Materials Type with Different Pyrolysis Temperature Level

On figure 3 it can be seen that liquid smoke density from coconut shell from raw materials on pyrolysis treatment 200oC and cinnamon on pyrolysis treatment 100oC has similar density at 1.0467 mg/ml is higher compared with other treatments. This result is suspected to have close relationship with liquid smoke rendement-content. Pyrolysis on temperature 400oC has lignine decomposition that when a material consists too many lignine factions then it will increase the produced rendement. Temperature 300°C is selected as the burning temperature, because on the temperature of 300°C, decomposed cellulose component produces organic acids and some phenol compound [9], [23]. Note : SK = Coconut fibre, TK = Coconut shell, KM=cinnamon T1 = 100±10oC, T2 = 200±10oC, T3 = 300±10oC, T4 = 400±10oC Burning temperature of 300°C produces better liquid smoke * Superscript letter that different on average column shows actual quality compared to temperature 500°C because it causes difference (P<0,05), fewer undesired ter [5]. **Quoted from Yatagai (2002) Liquid smoke density value is greater from the result of

research done by Nurhayati [18], ranged between 1,004-

308 1.018 and Komarayati research [20] with range between relatively the same. This condition is usually closely 0.97-0.99. However, this research result on density value is associated with the volume of initial raw materials water- smaller compared with the result of research done by content. Pyrolysis on temperature that is too high and the Nurhayati and Adelina [19] that is ranged between 1.085 to time that is too long will decrease the formation of liquid 1.095 (Table 4). Measurement result of liquid smoke density smoke. This is in accordance with the statement of Demirbas as the result of different raw materials treatment combination [24] that wood material pyrolysis process liquid smoke result with pyrolysis temperature produces greater average density can be produced maximally if the condensation process from 1.005. It means that the result has closely approach the happens perfectly. The difference of smoke distillation result of Yatagai’s research [22]. rendement amount is caused by the fact that the higher 2) Rendement (%): Liquid smoke rendement is a content of water in raw materials then the higher the percentage of the liquid smoke amount that is produced by a produced smoke distillation rendement amount and the raw material through pyrolysis process to the weight of raw longer the condenser then the chances to condition the materials before the beginning of pyrolysis. Total liquid imperfect burning result in process of smoke distillation smoke rendement that is produced on pyrolysis process extraction will be more optimal [16]. really depends on raw materials type that is used. Rendement Liquid smoke rendement that is produced on this research percentage that is acquired also relies heavily on pyrolysis is lower compared to the result of liquid smoke acquired by temperature that is used. The result of research on Table 2 Tranggono et al. [12] on pyrolysis of several wood types shows that cinnamon raw materials combination with with temperature range of 350-400°C produce liquid smoke pyrolysis temperature 400oC statistically does not have with average rendement of 49.1%. The total liquid smoke actual difference with treatment combination of pyrolysis rendement produced on pyrolysis process really depends on temperature 300oC, 200oC and 100oC and produce the raw materials type that is used. The acquired rendement highest liquid smoke rendement compared to the other two percentage also really depends on condensation system that materials. The high rendement value is supposedly that on is used. This condition is in accordance with Tranggono et al pyrolysis temperature of 400oC, lignine decomposition [12], that for the formation of liquid smoke, water is used as happens so that if the material consists lots of the lignin a cooling medium so that the heat exchange process can fraction, then it will increase the produced rendement. The occur fastly. Pyrolysis on temperature that is too high and difference of rendement percentage that is acquired is caused the time that is too long will reduces the formation of liquid by the diverse lignin and cellulose contents of each material smoke. This is in accordance with the statement of Demirbas among others 38.98 - 63.09% to cellulose and 19.35 - [24] that liquid smoke by wood material pyrolysis process 50.44% to lignine [12]. The high and low of liquid smoke can be produced maximally if the condensation process rendement on pyrolysis process is influenced by several happens perfectly. factors, such as climate, season, age of the plant, type of the 3) Analysis of Color (L, a, b) (HunterLab ColorFlex EZ plant, raw materials and way of burning. Figure of liquid spectophotometer): Liquid smoke raw materials treatment smoke rendement average (%) on raw materials treatment combination liquid smoke color with pyrolysis temperature combination with different pyrolysis temperature like figure was measured by using equipment HunterLab ColorFlex EZ 4 below. that produces value L, a* (-), and b* (+). L value shows the colour brightness, a* (-); greenish, b* (+); yellow, the higher the value of L (Lightning) shows that liquid smoke becomes brighter, the higher the value of b* (+) the colour of liquid smoke becomes more yellow, the higher the value of a* (-) the colour of liquid smoke becomes more green. The result of research shows that the brightness (L) from coconut shell liquid smoke on different pyrolysis temperature of (+) 3.81 with value a*: (+) 0:09 and b* (+) +1.91, then brightness (L) on coconut fibre liquid smoke on different temperature pyrolysis of (+) 3.65 with the value of a* (-) 0:24 and b* (+) 1:52 and also brightness (L) of cinnamon liquid smoke on different pyrolysis temperature (+) 3,11 with the value of a* (-) 0.06 and b* (+) 1:38 after being converted according to Figure information, the colour is around brownish-yellow. Fig. 4 Rendement Average (%) from Several Type Liquid Smoke Maker The brightness of liquid smoke is less white. Liquid smoke Raw Materials with Different Level of Pyrolysis Temperature as the result of pyrolysis with different temperature on average has reddish-brown colour. This is caused by the Liquid smoke production result on pyrolysis with content of tar compound that basically has black colour and temperatures of 400°C on cinnamon raw materials has the components that have high molecular weight, therefore there highest rendement value (38.78%) while the lowest value on will be further research for purification process with intent to coconut fibre raw materials on pyrolysis temperature of produce liquid smoke with clearer colour and no poison, so 100°C by 24.26%. However, coconut fibre liquid smoke o when applied on food material, it will produce interesting, rendement on pyrolysis temperature of 100 C does not have not dark smoked product colour. The difference of liquid actual difference with pyrolysis temperature on 200oC, o o smoke colour from each faction is influenced by the 300 C and 400 C and all treatment show that the result is presence of tar. Coconut fibre liquid smoke has the darkest

309 colour because on that temperature, there is possibility of tar yellowish colour. The figure of average colour (b) liquid entrainment, while somewhat reddish-brown is from smoke on raw materials treatment combination with cinnamon liquid smoke. The analysis result of this liquid pyrolysis temperature can be seen in Figure 7 below. smoke colour is rather different with liquid smoke colour from coconut shell that on the fraction I light yellow and fraction II whitish-yellow [25]. This is because liquid smoke consists of 1.45% phenol compound. The emergence of brownish yellow colour might be due to the fact that liquid smoke consists of phenol compound [26]. In Judd-Hunter, the colour can be represented by L (light or dark, 0 = perfect black to 100 = perfect white), a (-a = greenish, + a = reddish) and b (-b = blueish, + b = yellowish). 4) To analysis the brightness (L) value diversity of liquid smoke maker raw materials combination with different pyrolysis temperature shows that there is no interaction with the value of P< 0.05. Figure of average colour (L) liquid smoke on raw materials treatment combination with Fig. 6 The Average of colour (a) from Several Liquid Smoke Maker Raw Materials Type with Different Pyrolysis Temperature Level pyrolysis temperature shown in figure 5 below.

Fig. 7 The Average of Colour (b) from Liquid Smoke Maker Different Raw Materials Type with Different Pyrolysis Temperature Level

Fig. 5 The Average of Colour (L) from Several Liquid Smoke Maker Raw Liquid smoke colour is affected by pyrolysis temperature Materials Type with Different Pyrolysis Temperature Level that causes degradation (cellulose, hemicellulose and lignin).

It is reinforced by the result of research from Wijaya [27] For colour a (Table 2) has range from value + 0.43 to – that temperature change cause the colour change on liquid 0.31, it means from greenish until approaching reddish smoke. The higher pyrolysis temperature then the darker the colour, and statistically treatment combination of liquid colour of produced liquid smoke. In the similar aspect, wood smoke raw materials with pyrolysis temperature shows that liquid smoke is the brownish-yellow/darkish-brown colour there is real interaction (appendix 5e), further on test HSD liquid acquired from side-result of making charcoal [20]. It 5% on table 2 above shows liquid smoke raw materials was confirmed by Girard [9] that on temperature 200-450oC treatment combination from coconut shell on pyrolysis there is hemicellulose, cellulose and lignin degradation in temperature of 100oC does not have actual difference with wood. Liquid smoke colour in the result of this research is pyrolysis temperature of 400oC because from the colour, almost the same with the result of research by Komarayati, both show equally approaching greenish colour, it has actual [20] with brownish-yellow colour, but it will be different difference with pyrolysis temperature of 200oC and 300oC from the result of research done by Nurhayati [18] and and from terms of colour, both are similarly leads to reddish Nurhayati and Adalina [19], which is darkish-brown colour. colour. Figure of average colour (a) liquid smoke on Liquid smoke colour with bright colour have better quality treatment combination with raw materials with pyrolysis compared with liquid smoke with dark colour. Liquid smoke temperature like figure 6 below. colour in the result of this research fulfils the quality of For colour b (Table 2) ranges from values +1.03 to +2.81, Japanese liquid smoke specification. Transparency of it begins to approach yellowish colour, and statistically cinnamon liquid smoke on pyrolysis temperature 400oC is treatment combination of liquid smoke raw materials with transparent so that it meets the quality standards of Japanese pyrolysis temperature shows that there is actual interaction, liquid smoke specification (Table 2). The result of this further on test Tukey 5% on Table 2 shows treatment research is similar with the result of research done combination of liquid smoke raw materials from coconut Komarayati [20] that the transparency of wood liquid smoke shell on pyrolysis temperature of 100oC has no actual is not cloudy or transparent. The more transparent liquid difference with pyrolysis temperature 200oC, there is actual smoke, the better the quality of that liquid smoke. difference with pyrolysis temperature to 300oC and 400oC and from the terms of colour both are equally approach

310 C. Chemical Characteristic of Liquid Smoke has started, and the higher pyrolysis temperature, liquid Chemical characteristics from result of research of liquid smoke pH has tendency to decrease. smoke production from several raw materials that consists of On pH values on average variance analysis shows the coconut fibre, coconut shell and cinnamon with different result of actual interaction (P <0.05) between treatment A pyrolysis temperature as in Table 3 below. and treatment B. Figure of liquid smoke pH condition on treatment combination of raw materials with pyrolysis TABLE III temperature like in figure 8 below. THE AVERAGE OF CHEMICAL CHARACTERISTIC ON DIFFERENT RAW MATERIALS TREATMENT COMBINATION LIQUID SMOKE DIFFERENCE WITH DIFFERENT PYROLYSIS TEMPERATURE

Fig. 8 Graphic of Liquid Smoke pH Average Value from Several Raw Materials Type with Different Temperature Level

The average of pH values in figure 8 shows that in pyrolysis temperature of 1000C-3000C for raw materials of coconut shell and cinnamon is lower than the result from coconut fibre raw materials. It is suspected that pH value is closely related with hemicellulose fractions decomposition that produce acetic acid, in accordance with Sutin research Notes : SK = Coconut fibre, TK = Coconut shell, KM=cinnamon T1 = 100±10oC, T2 = 200±10oC,T3 = 300±10oC, T4 = 400±10oC [16] mentions that coconut shell has hemicellulose * The different superscript letter on average column shows the component and cellulose bigger than coconut fibre so that actual difffrence P<0,05) the amount of acid is produced bigger. Hemicellulose and **Quoted from Yatagai (2002) cellulose are wood components that if it is decomposed, it

will produce organic acid compounds such as acetic acid. 1) pH: The principle in testing degree of acidity (pH) by Besides it is also caused by the liquid smoke density level using pH meter equipment is a pH measurement method produced where liquid smoke from coconut fibre raw based on hydrogen ion activity measurement materials is the lowest compared to the other two raw potentiometrically/electrometrically by using pH-meter. materials shown by liquid smoke density is successively Before using, pH-meter equipment is calibrated with buffer 1.00; 1.02; and 1.01. This result is in accordance with the solution according to equipment instruction on every research of Haji, et. al. [17] that the average of pH value on measurement. three treatment combination shows the result of average pH Result of further test on HSD 5% in tabel 2 shows that values in liquid smoke produced on organic waste pyrolysis coconut fibre liquid smoke produces the lowest pH on process has tendency to diverse according to the variation of pyrolysis temperature level 3000C± 10oC compared to liquid water-content of each used raw materials. smoke pH from two other raw materials with different In liquid smoke pH value, the lower is better because its pyrolysis temperature. Statistically liquid smoke pH with antibacterial force also becomes higher. The result of treatment combination of coconut fibre with pyrolysis research shows that liquid smoke pH from pyrolysis of three temperature 100 ± 10oC does not have actual difference with raw materials on four different temperature ranges 2,57- 4.82. pyrolysis temperature 2000C ± 10oC, actual difference with If pH value is low, it means that produced smoke has high temperature 3000C± 10oC and temperature 4000C ±10oC. quality, especially in terms of using as food preservatives While on coconut shell liquid smoke pH on treatment [18]. The low pH value can entirely influence to the value of combination with pyrolysis temperature 100± 10oC does not product smoke or organoleptic characteristic durability and have actual difference with 200±10oC, then actual difference storability. Because of that low pH on microbes or bacteria with temperature 300± 10oC and 400± 10oC. Next on as the obstruction in preservatives process tend not to cinnamon liquid smoke on treatment combination with survive and breed. In accordance with the explanation Haji pyrolysis temperature 100±10oC has actual difference with et al, [17], measurement of pH values in liquid smoke is 200± 10oC, then it also has actual difference with intended to know the level of raw materials decomposition temperature 300± 10oC and 400± 10oC. Statistically, the process by pyrolysis. The low pH value can have overall difference on coconut fibre liquid smoke with different influence to the value of durability and storability of a temperature pyrolysis supposedly on pyrolysis temperature product. The liquid smoke pH value in this research result, above 100oC the component decomposition of liquid smoke the average pH is almost similar if compared with the result

311 of research by Nurhayati [18], about 4.3-4.7, Nurhayati and such as depending on the type of raw materials, wood water- Adalina [19] about 3.2-3.8 then Komarayati, [20] about 3.2- content, and pyrolysis temperature. Water-content of 6.80. But it is bigger from the result of research done by coconut shell after pyrolysis on temperature 400oC is 3.28%, Amperawati [21] with pH value ranges from 2.91. For the coconut fibre with temperature 400oC is 9.00% and range of liquid smoke PH measurement result on different cinnamon with temperatures 300oC is 6.61%. raw materials treatment combination with pyrolysis On Figure 9, it also can be seen that on pyrolysis temperature is associated with liquid smoke quality temperature 300oC on coconut shell raw materials shows an standards from Yatagai [22] on average it is in the range of increase in the titrated acid value. This is due to the 1.5-3.7. Especially to coconut fibre with different pyrolysis temperature 300°C, cellulose and hemicellulose components temperature that produces greater pH than result of research is decomposed to form acid compounds. This is in from Yatagai [22]. accordance with the research by Luditama [5] that tries to compare the best burning process condition to produce liquid 2) Total acid (%): Liquid smoke total acid variance smoke from coconut shell and coconut fibre by using analysis can be seen in attachments 6a, shows that there is no temperatures of 300°C and 500°C. Based on that research, it interaction between treatment combinations of liquid smoke can be seen that temperatures of 400°C can produce liquid raw materials with pyrolysis temperature. In this conditions, smoke with better quality. Besides, on temperatures of there will be no further tests. The figure of titrated acid- 400°C, it also produced lower tar compound where tar is the content average can be seen on figure 9 below. compound that must be removed to produce liquid smoke with better quality. The quality from liquid smoke is also determined by the purity from the compounds. Liquid smoke consists of compound acid group and its derivatives, alcohols, aldehydes, hydrocarbons, ketones, phenols and pyridine [28]. Acids do not have specific influence but it has general effect on the overall organoleptic quality [9]. The acid products and its derivatives have potential as natural preservatives [27]. Furthermore, acetic acid and furan begin to form on pyrolysis temperature of 260°C as the result from hemicellulose degradation [23]. Wood pyrolysis experiences gradual decomposition, that is the hemicellulose is degraded on temperature 200-260oC [29]. The range of acidity values that is acquired (0.12%-1.62%) is lower to the result of Fig. 9 Graphic of Liquid Smoke Titrated Acid Total from Several Type of research of Darmadji [15], Kadir, (30), Amperawati, [21] Raw Material with Different Pyrolysis Temperature Level and Apituley and Darmadji [31]. The result of research meet From the observation result on table 3 and figure 9 above, the quality standards of Japanese liquid smoke specifications. the average of titrated result acid ranges between 0.06 to 3) Phenol-Content (%): Result of variance analysis 0.97%, for the average of total acid, coconut fibre is the shows that liquid smoke raw materials difference treatment lowest and the average of total acid for coconut shell is the combination with pyrolysis temperature gives influence of highest. The diversity analysis result shows that there is no significant actual difference to phenol-content (P<0:01). real interaction (P> 0.05) between liquid smoke raw Liquid smoke phenol-content data (Table 3) shows treatment materials treatment with pyrolysis temperature level to combination of coconut shell material with pyrolysis titrated acid total, it can be seen that the total value of temperatures of 400°C shows the highest phenol-content titrated acid is higher on the treatment combination of compared to both of others raw materials. Statistically (P coconut shell on pyrolysis temperature 300oC at 0,97% o <0.05) treatment combination of coconut shell with compared with coconut fibre on pyrolysis temperature 300 C o o temperatures of 400 C has actual difference with treatment at 0.03% and cinnamon on pyrolysis temperature 300 C of combination of temperature to 300oC, 200oC and 100oC. The 0.51%. The tendency of acid total value on combination of high value of phenol-content on coconut shell depends on coconut fibre raw materials with the increasing of pyrolysis raw materials condition. This is in accordance with the temperature becomes lower. The same thing also happens on opinion by Girard [9] who mentions that the composition of cinnamon raw materials, it shows that the more pyrolysis chemical substances that are contained in liquid smoke can temperature increases then the tendency of total acid value be influenced by several factors, such as: type of wood or decreases, this is different with combination of coconut shell raw materials that is used, water-content from material, raw materials with different temperature, it does not shows burning temperature, burning duration, condensation such phenomenon. temperature and purification type that is done. Phenols- This difference is because the different raw materials content on liquid smoke usually has range between 0.2 - types is used, difference pyrolysis temperature and water- 2.9% [23]. For the analysis result of phenol-content from the content on raw materials. This is in accordance with the three raw materials above almost all of them range between opinion from Darmadji [15], he mentions that pyrolysis 0.2 - 2.9% except for coconut fibre material that is pyrolyzed process on wood constituents such as cellulose, on temperature of 100oC and 400oC. Phenol is the result of hemicellulose and lignine will produce organic acid, phenol, wood component disintegration, which is lignin. The more carbonyl as the compounds that have important role in food of lignin content in the wood, then the greater of phenols- preservatives. Those compounds have different proportions, content on liquid smoke. The quantity and quality of phenol

312 compound that can be found on liquid smoke is related with influence of significant actual difference to carbonyl-content lignin-content and pyrolysis temperature [9]. Furthermore, (P<0:05). o lignin degradation occurs on temperature 310-500 C, when Liquid smoke carbonyl-content like on table 3 shows that that temperature has not been reached then it will influence cinnamon treatment combination with pyrolysis temperature lignin degradation and phenol content from liquid smoke of 200oC gives the result of highest carbonyl-content that is produced [23]. The range of values from the result of compared to both of other raw materials. Statistically research that is acquired (0.17% - 1.73%) is lower than the (P>0.05) cinnamon treatment combination with temperature result of research done by Kadir [30], that phenol-content of 200oC has actual difference with the treatment acquired on hybrid coconut shell liquid smoke of 4,71%. combination of temperature 300oC, 400oC and 100oC. The The value of phenol-content of this research is smaller than high value of carbonyl-content on cinnamon depends on raw the result of research done by Darmadji [15] with the range materials. This is in accordance with the opinion of Girard of phenol-content from 2.11 - 3.13. But smaller than the [9], he mentions that composition of chemical substances result of research by Amperawati [21] with phenol-content that are contained in liquid smoke can be influenced by of 12.29%. Table 4 is provided with some researches related several factors such as: type of wood or raw materials that is with liquid smoke quality. The result of this research is to used, water-content from material, burning temperature, compare the result of research on liquid smoke quality from burning duration, temperature condensation and purification coconut fibre, coconut shell and cinnamon raw materials type that is done. On carbonyl content of liquid smoke below. usually has range between 2.6 - 4.6% [23]. For the analysis result of carbonyl-content from the three raw materials TABLE IV THE COMPARISON OF LIQUID SMOKE QUALITY FROM DIFFERENT RAW above almost all range between 2.6 - 4.6%, except for MATERIALS TREATMENT COMBINATION WITH PYROLYSIS TEMPERATURE coconut fibre material that is pyrolyzed on temperature of WITH SEVERAL RESULT OF RESEARCH 100oC, 200oC, 300oC and 400oC. For figure of raw materials treatment combination with pyrolysis temperature can be seen in figure 11 below. The average of carbonyl result on figure 11 shows carbonyl-content of cinnamon liquid smoke is greater compared to coconut shell and coconut fibre raw materials. Cellulose degradation process occur on temperatures 280- 320°C, Cellulose degradation produces acetic acid compound and carbonyl compound [9]. This is also clarified by Sjostrom [29] that wood cellulose experiences decomposition on temperature of 240-350oC. The range of carbonyl-content value that is acquired (1.056% - 4.6767%) is smaller than the range of value from several results of researches, Darmadji [15] has range between 9.30 - 17.14%, Kadir [30] with 13.19% and Amperawati [21] with 12.29%, it is also smaller from the result of research by Apituley and Darmadji [31], with carbonyl-content of liquid smoke from sago cortex by 10.05% (Table 4).

For figure of raw materials treatment combination with pyrolysis temperature can be seen on figure 10 below.

Fig. 11 The Average of Carbonyl-Content Value (%) from Several Raw Materials Type with Different Pyrolysis Temperature Level

Fig. 10 The Average of Phenol-Content Value (%) from Several Raw Materials Type with Different Pyrolysis Temperature Level 5) Benzo(a)pyren-Content from Liquid Smoke: The result of variance analysis shows that treatment combination of different liquid smoke raw materials with different pyrolysis 4) Carbonyl-Content (%): The result of variance analysis temperature shows the real influence to benzo(a)pyren- shows that liquid smoke of different raw materials content from liquid smoke (P<0:01). Further on Table 3 combination treatment with pyrolysis temperature shows

313 above shows that the result analysis of benzo(a)pyren- coconut shell and coconut fibre materials on pyrolysis content from coconut fibre, coconut shell and cinnamon raw temperature of 400oC materials show that liquid smoke from pyrolysis temperature o of 400 C on cinnamon has the lowest value (<0.04) ACKNOWLEDGMENT compared with liquid smoke from the other materials. This We would like to thank Directorate General of High result indicates that cinnamon consists lower benzo(a)pyren- Education, Ministry of Education, in correspond to content in the process of pyrolysis. The higher of pyrolysis Implementation Agreement of Competitive Research Grant, temperature on cinnamon raw materials, the tendency of National Priority, Rector of Ekasakti University, The Head benzo(a)pyren-content will decrease. It is suspected that the of LPPM Ekasakti University, The Dean of Agriculture higher temperature, it will decompose the compounds in Faculty Ekasakti University, Supervisors of Andalas cinnamon. For liquid smoke security as food preservatives University, Bung Hatta University and Laboratory team and material, the effort needs to be taken so that benzo(a)pyren- staff that have provided help in this activity. content as small as possible because this compound is very dangerous for humans with its carcinogenic nature. Figure of REFERENCES benzo(a)pyren-content on raw materials treatment combination with pyrolysis temperature can be seen in figure [1] Pszczola DC. Tour Higligts Production and Uses if Smoke base flavors-food tech (49):70-74. 1995 12 below. [2] Tsamba, A. J., Yang, W., & Blasiak, W. Pyrolysis characteristics and global kinetics of coconut and cashew nut shells. Fuel Processing Technology,87(6), 523-530. 2006 [3] Darmadji P. 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